EP0039794B1 - Dispersions anioniques, procédé pour leur préparation et leur utilisation comme agents d'encollage superficiel pour papier - Google Patents

Dispersions anioniques, procédé pour leur préparation et leur utilisation comme agents d'encollage superficiel pour papier Download PDF

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Publication number
EP0039794B1
EP0039794B1 EP81102874A EP81102874A EP0039794B1 EP 0039794 B1 EP0039794 B1 EP 0039794B1 EP 81102874 A EP81102874 A EP 81102874A EP 81102874 A EP81102874 A EP 81102874A EP 0039794 B1 EP0039794 B1 EP 0039794B1
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Prior art keywords
polymerization
weight
water
solution
ethylenically unsaturated
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EP81102874A
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German (de)
English (en)
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EP0039794A1 (fr
Inventor
Konrad Dr. Richter
Lothar Dr. Hoehr
Fritz Dr. Reichel
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic

Definitions

  • DE-A-2 548 393 sizing agents for the mass and surface sizing of paper based on anionic polymers in dispersion form are known, which are obtained by 10 to 60 parts by weight of a solution copolymer from 30 to 90 weight percent of a nonionic ethylenically unsaturated monomers and 70 to 10 percent by weight of an ethylenically unsaturated C 3 to C 5 carboxylic acid and / or maleic anhydride and, to a lesser extent, also monomers containing sulfonic acid groups, 90 to 40 parts by weight of a mixture of ethylenically unsaturated copolymerizable monomers which, on their own, polymerize hydrophobic Form copolymers with a glass transition temperature between + 60 and - 40 ° C, grafted on.
  • dispersions with high solids contents are obtained which result in a relatively low viscosity and alkali-stable sizing, but are sufficiently shear-stable only in the alkaline medium for use in the size press.
  • DE-A-2163 850 discloses a process for the surface sizing of paper and cardboard, in which aqueous dispersions of copolymers of 15 to 60 percent by weight of a nitrile of a, ⁇ -olefinically unsaturated carboxylic acid and other olefinically unsaturated monomers are used as sizing agents.
  • these copolymer dispersions also have sufficient shear stability only in the alkaline medium in order to be able to withstand the mechanical stress in the size press nip without coagulation.
  • this severely limits the applicability of these dispersions because, for example, it is not possible to combine them with acid-reacting substances, such as liquid acid dyes.
  • the object of the invention is to provide an anionic dispersion which, for. B. can be used as a surface sizing agent for paper and its sizing effect and processability is largely independent of the pH of the preparation solution.
  • the anionic dispersions according to the invention are low-foaming and are suitable as surface sizing agents for paper, while maintaining their sizing effect and stability regardless of the pH of the preparation solution. You can also use products containing formaldehyde, e.g. B. urea-formaldehyde or melamine-formaldehyde resins can be combined.
  • the sizes produced with the anionic dispersions according to the invention are resistant to alkalis. It is also possible to glue paper with a wide variety of fiber and filler compositions and with different alum or acid content. In particular, neutral sizing is alum-free, e.g. B. calcium carbonate-containing papers possible.
  • the polymerization takes place in a water-miscible solvent.
  • solvents are monohydric alcohols with 1 to 4 carbon atoms, ethanol, n-propanoi, isopropanol, Ethylene glycol monomethyl ether or dimethylformamide.
  • n-propanol and iso-propanol are used as solvents.
  • the solvents can contain up to 30 weight percent water.
  • nonionic ethylenically unsaturated monomers of group a) are alkenes with 2 to 10 carbon atoms, preferably those with a terminal double bond, such as ethylene or diolefins, in particular butadiene and isoprene, and vinylaromatic monomers, for.
  • Suitable monomers in this group are also carboxylic acid esters of ethylenically unsaturated C 3 - to C s -mono- and dicarboxylic acids and monohydric alcohols with 1 to 18, preferably 4 to 12 carbon atoms, the nitriles of the carboxylic acids mentioned, and vinyl esters of 1 to 12 carbon atoms containing aliphatic Carboxylic acids. From this group of monomers, preference is given to using styrene, n-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, lauryl acrylate, acrylonitrile, methylacrylonitrile, vinyl acetate and vinyl propionate.
  • amides or substituted amides of a, ⁇ -ethylenically unsaturated mono- or dicarboxylic acids for.
  • B acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diethylaminomethylacrylate, diethylaminoethyl acrylate, dimethylaminopropylacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • the compound of formula 11 is preferably used as the monomers of group b) or
  • Some of the monomers containing sulfonic acid groups can be replaced by ethylenically unsaturated mono- and / or dicarboxylic acids or half-esters of dicarboxylic acids. If carboxylic acids are used in the polymerization, they are only present in minor amounts, in this case the monomer mixture of components a) and b) contains up to 4% by weight of copolymerizable ethylenically unsaturated carboxylic acids.
  • the solution polymerization of the monomers a) and b) takes place at temperatures from 20 to 160, preferably 60 to 140 ° C.
  • the water-miscible solvent used in solution polymerization can contain up to 30 percent by weight of water. In general, the content of water in solvent is between 6 and 15 percent by weight.
  • a limitation for the water content of the water-miscible solvent results from the monomer composition and from the fact that a homogeneous solution of a copolymer is produced in the first polymerization stage.
  • the concentration of the polymer in this homogeneous solution can vary within a wide range, e.g. B. between 70 and 20 weight percent.
  • the homogeneous polymer solution is then diluted with water in a weight ratio of 1: 3 to 1:50. Due to the content of sulfonic acid groups in the polymer, it is clearly soluble in the mixture of the water-miscible solvent in which the polymerization was carried out and the added water.
  • the concentration of the solution polymer in the solution diluted with water is in the range from 2 to 25 percent by weight.
  • the aqueous polymer solution, from which the water-miscible organic solvent can optionally be distilled off, serves as a template for the second polymerization stage, in which nonionic ethylenically unsaturated monomers are polymerized in the manner of an emulsion polymerization. Based on 1 part by weight of the solution polymer, 1 to 4 parts by weight of a nonionic ethylenically unsaturated monomer or a mixture of the monomers is used.
  • Suitable nonionic ethylenically unsaturated monomers are all those monomers which are used as monomers of group a) for the preparation of the solution copolymer.
  • Styrene, C 4 -C 8 -alkyl acrylates and methacrylates, such as butyl esters of acrylic acid and methacrylic acid, hexyl acrylate and 2-ethyl-hexyl acrylate, acrylonitrile or vinyl acetate are preferably used.
  • the emulsion polymerization takes place in the temperature range from 40 to 150 ° C., preferably 60 to 100 ° C., using customary amounts of water-soluble polymerization initiators.
  • the upper limit for the polymerization initiators is 4 percent by weight, based on the monomers to be polymerized.
  • Suitable polymerization initiators for emulsion polymerization are, for example, peroxides, hydroperoxides, hydrogen peroxide and inorganic peroxides, e.g. B. hydrogen peroxide, potassium peroxodisulfate but also redox systems, such as. B. potassium peroxodisulfate / addition products of bisulfites to aldehydes and tert-butyl hydroperoxide / ascorbic acid.
  • the emulsion polymerization is preferably carried out in the absence of emulsifiers, but emulsifiers can additionally be used in an amount of up to 3 percent by weight, based on the polymer.
  • emulsifiers are, for example, nonionic emulsifiers which are obtained by ethoxylating phenol or phenol derivatives, e.g. B. octylphenol or nonylphenol can be obtained.
  • Such emulsifiers contain 4 to 30 moles of ethylene oxide per mole of phenol.
  • anionic emulsifiers are suitable, for example, alkyl sulfonates, such as sodium dodecyl sulfonate, sodium lauryl sulfonate, alkyl sulfates, alkylbenzenesulfonic acids or their salts or alkylarylsufonates.
  • alkyl sulfonates such as sodium dodecyl sulfonate, sodium lauryl sulfonate, alkyl sulfates, alkylbenzenesulfonic acids or their salts or alkylarylsufonates.
  • the mixtures of nonionic and anionic emulsifiers can also be added to the dispersion after the emulsion polymer has been prepared. Based on the dispersed polymer, 0.05 to 3 percent by weight of an emulsifier or mixture of emulsifiers is used. Stable anionic dispersions are obtained which are used for the surface sizing of paper.
  • the sizing agent according to the invention is adjusted with water to the concentration that is just required for paper sizing, for example to a polymer content of 0.05 to 1.0 percent by weight, based on the preparation solution.
  • the amount of copolymer. that is applied to the paper for sizing is usually between 0.02 and 3, preferably between 0.3 and 0.8 percent by weight, based on dry paper stock.
  • the anionic dispersions the solids content of which can be up to 50 percent by weight, are diluted with water.
  • the preparation solutions can also contain other auxiliary substances. e.g. B. starch, dyes, wax emulsions and resin glue.
  • the anionic dispersions according to the invention are effective as sizing agents in the entire pH range and do not need to be adjusted to a specific pH. However, it is possible to partially or completely neutralize the dispersions with sodium hydroxide solution, potassium hydroxide solution or ammonia or amines and to use them in this form as sizing agents.
  • the dispersions according to the invention are used as surface sizing agents in the customary manner, ie. H. usually in combination with starch or synthetic dry strength agents, whereby the preparation solution is usually applied to the paper using a size press. It is of course also possible to spray the preparation solution by spraying or dipping or z. B. with the help of the water scraper on the paper webs. The paper treated with the preparation solution is then dried. The glue is already fully developed after drying.
  • the dispersion in 0.01% strength aqueous solution is measured in a cuvette with an edge length of 2.5 cm using light of the wavelength 546 nm.
  • the particle diameter can be calculated (cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague 1976, Edice Marco, Rada D-DATA, SVAZEK D -1).
  • the resulting anionic dispersion had a solids content of 32% and an LD value of 99.
  • the preparation was carried out as for dispersion 4, except that 23 parts of styrene, 8.9 parts of methacrylamido-propanesulfonic acid and 2.35 parts of azoisobutyronitrile, dissolved in 33 parts of dimethylformamide, were heated to 85 ° C. for the prepolymer. After 30 minutes, a further 0.6 parts of the initiator were added. After a further 90 minutes, the prepolymer was dissolved in 205 parts of water and, as in Example 4, the following emulsion polymerization was carried out.
  • the anionic dispersion 5 had an LD value of 96 at a solids content of 33.1%.
  • the prepolymer was prepared under the conditions given in Example 1 from 40 parts lauryl acrylate, 16 parts 2-acrylamido-2-methyl-propanesulfonic acid, 40 parts isopropanol, 4.8 parts Water and 4.0 parts of azoisobutyronitrile.
  • 67 parts of styrene and 37 parts of ethylhexyl acrylate, and 1.3 parts of potassium persulfate were used.
  • the anionic dispersion had an LD value of 94 at a solids content of 28.7%.
  • the prepolymer was prepared from 13 parts of 2-acrylamido-2-methyl-propanesulfonic acid, 25.8 parts of styrene, 32.4 parts of isopropanol, 3.9 parts of water and 3.3 parts of azoisobutyronitrile.
  • 72 parts of styrene and 40 parts of isobutyl acrylate were added.
  • the result was an anionic dispersion with a solids content of 29% and an LD value of 98.
  • comparative dispersion 1 was prepared by polymerizing 67 parts of butyl acrylate, 30 parts of acrylonitrile, 3 parts of methacrylic acid and 3 parts of sodium dodecyl sulfonate as an emulsifier in water to give an anionic dispersion with a solids content of 30% by weight.
  • the LD value was 99.
  • a dispersion was prepared by polymerizing a monomer mixture of 67 parts of butyl acrylate, 30 parts of acrylonitrile, 4.5 parts of vinylsulfonic acid and 3 parts of sodium dodecylsulfonate as emulsifier.
  • An anionic dispersion with a solids content of 40% by weight was obtained.
  • the LD value was 92.
  • a dispersion was prepared by preparing a solution polymer from 130 parts of styrene, 50 parts of acrylic acid and 20 parts of maleic anhydride at 85 ° C., adjusting it ammoniacally and, in addition, a mixture of 300 parts of isobutyl acrylate and 300 Parts of acrylonitrile polymerized at 85 ° C.
  • the dispersions described above were checked for their sizing effect.
  • a non-glued, wood-free offset paper containing 14% ash and 1% alum served as the test paper.
  • the weight per unit area was 70 g / m 2
  • the degree of grinding was 25 ° SR (degree of grinding measured according to Schopper-Riegler, see Ullmanns Encyklopadie der Technische Chemie, 3rd edition, Urban & Schwarzenberg, Kunststoff-Berlin 1962, volume 13, pages 123 and 124 ).
  • the preparation solutions each contained 6 g / l of polymer, based on the solids content of the dispersions and 60 g / l of an oxidatively degraded potato starch. The liquor absorption was 90% in all cases, based on dry paper.
  • the dispersions 1 to 7 according to the invention are compared in the table below with the comparative dispersions 1 to 4. (Dispersion 1 was used in Example 1, dispersion 2 in Example 2, etc.).
  • the sizing preparations described above were also tested for stability on an experimental paper machine.
  • anionic dispersion 1 the preparation solution was heated to a temperature of 60 ° C. and used to glue paper. After a running time of 40 minutes, no deposit formation was found on the size roller application rollers.
  • comparative dispersion 1 the preparation solution was heated to a temperature of 30 ° C. and used as a sizing agent. Deposits appeared on the size press roller after only 15 minutes. The experiment was repeated, but the preparation solution was adjusted to a pH of 9. At a temperature of 30 ° C this preparation solution could be applied to the paper without being deposited on the rollers, but at a temperature of 60 ° C the rollers of the size press were already occupied after 10 minutes.
  • the preparation solution which contained the comparison dispersion 2 as a sizing agent, also showed deposits on the rollers of the size press as soon as the preparation solution was heated to a temperature of 60.degree.
  • the preparation solution which contained the comparative dispersion 3 as a sizing agent, also proved to be stable in the stability test at 60 ° with weakly acidic papers. However, if strongly acidic papers were impregnated, a size press coating gradually formed after 30 minutes because the pH of the preparation solution dropped.
  • Comparative dispersions 1-2 according to DE-A-21 63850 and comparative dispersion 3 according to DE-A-2548393 are therefore clearly inferior to the anionic dispersion according to the invention in terms of sizing effect and / or stability.
  • a non-sized, wood-free offset paper that contained 14% ash and 1% alum and had a basis weight of 70 g / m 2 (freeness 25 ° SR) was sized with a preparation solution containing 4.5 g / 1 polymer, based on the solids content of the anionic dispersion 1 and 60 g / l of an oxidatively degraded potato starch.
  • a preparation solution containing 4.5 g / 1 polymer based on the solids content of the anionic dispersion 1 and 60 g / l of an oxidatively degraded potato starch.
  • the Cobb values were tested with water and with sodium hydroxide solution of various concentrations. The following results were obtained:
  • the sizing of the dispersion according to the invention is therefore resistant to alkalis.
  • the anionic sizing agent 1 can be combined with a melamine-formaldehyde resin in such a way that neither the sizing nor the wet strength effect of the melamine-formaldehyde resin is impaired.
  • Samples of the paper specified in the example with the preparation solutions a) and b) were sized on the surface. The results found are summarized in the table.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)

Claims (7)

1. Dispersions anioniques qui sont préparées par polymérisation en deux étapes, un mélange de monomères à insaturation éthylénique non ioniques et de monomères à groupes acide sulfonique, insaturés éthyléniquement étant copolymérisé dans la première étape en donnant une solution homogène à la manière d'une copolymérisation en solution, en présence d'un initiateur de polymérisation soluble dans le mélange de monomères et, après dilution avec de l'eau, dans une seconde étape de polymérisation, étant polymérisé à la manière d'une polymérisation en émulsion, en présence de quantités usuelles d'initiateurs de polymérisation solubles dans l'eau, caractérisé par le fait que, dans la première étape de polymérisation, on copolymérise un mélange de monomères constitué de
a) 85 à 55 % en poids de monomères à insaturation éthylénique, non ionogènes, et
b) 15 à 45% en poids de monomères contenant des groupes acide sulfonique insaturés éthyléniquement,
en présence de 0,015 à 0,15 mole, par mole du mélange de monomères, d'un initiateur de polymérisation soluble dans le mélange de monomères, on dilue la solution polymère homogène avec de l'eau, en rapport en poids de 1 : 3 à 1 : 50 et, dans la deuxième étape de polymérisation, on polymérise, dans cette solution polymère, 1 à 4 parties en poids, rapportées à 1 partie en poids du polymérisat en solution, d'au moins un monomère insaturé éthyléniquement, non ionogène.
2. Dispersion anionique selon la revendication 1, caractérisé par le fait que, dans la première étape de polymérisation, on polymérise un mélange de monomères constitué par
a) styrène, méthacrylate de méthyle, acrylate d'éthylhexyle et/ou acrylate de lauryle et
b) acide 2-acrylamino-2-méthylpropanesulfonique..
3. Procédé de préparation des dispersions anioniques selon les revendications 1 et 2 par polymérisation en deux étapes, un mélange de monomères à insaturation éthylénique non ioniques et de monomères à groupes acide sulfonique, insaturés éthyléniquement étant copolymérisé dans la première étape en donnant une solution homogène, à la manière d'une copolymérisation en solution, en présence d'un initiateur de polymérisation soluble dans le mélange de monomères et, après dilution avec de l'eau, dans une seconde étape de polymérisation, étant polymérisé à la manière d'une polymérisation en émulsion, en présence de quantités usuelles d'initiateurs de polymérisation solubles dans l'eau, caractérisé par le fait que, dans la première étape de polymérisation, on copolymérise un mélange de monomères constitué de
a) 85 à 55 % en poids de monomères à insaturation .éthylénique, non ionogènes, et
b) 15 à 45% en poids de monomères contenant des groupes acide sulfonique insaturés éthyléniquement,
en présence de 0,015 à 0,15 mole, par mole du mélange de monomères, d'un initiateur de polymérisation soluble dans le mélange de monomères, on dilue la solution polymère homogène avec de l'eau, en rapport en poids de 1 : 3 à 1 : 50 et, dans la deuxième étape de polymérisation, on polymérise, dans cette solution polymère, 1 à 4 parties en poids, rapportées à 1 partie en poids du polymérisat en solution, d'au moins un monomère insaturé éthyléniquement, non ionogène.
4. Utilisation des dispersions anioniques selon les revendications 1 et 2 comme agents d'encollage en surface de papier.
EP81102874A 1980-05-12 1981-04-15 Dispersions anioniques, procédé pour leur préparation et leur utilisation comme agents d'encollage superficiel pour papier Expired EP0039794B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81102874T ATE4513T1 (de) 1980-05-12 1981-04-15 Anionische dispersionen, verfahren zu deren herstellung und deren verwendung als oberflaechenleimungsmittel fuer papier.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3018081 1980-05-12
DE19803018081 DE3018081A1 (de) 1980-05-12 1980-05-12 Anionische dispersionen fuer die oberflaechenleimung von papier

Publications (2)

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EP0039794A1 EP0039794A1 (fr) 1981-11-18
EP0039794B1 true EP0039794B1 (fr) 1983-08-24

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EP81102874A Expired EP0039794B1 (fr) 1980-05-12 1981-04-15 Dispersions anioniques, procédé pour leur préparation et leur utilisation comme agents d'encollage superficiel pour papier

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EP (1) EP0039794B1 (fr)
AT (1) ATE4513T1 (fr)
DE (2) DE3018081A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL246802A (fr) * 1958-12-27
BE789727A (fr) * 1971-10-06 1973-04-05 Calgon Corp Polymeres hydrosolubles d'acide 2-acylamido-2-methylpropane sulfonique
DE2548393A1 (de) * 1975-10-29 1977-05-12 Basf Ag Leimungsmittel fuer papier
US4065523A (en) * 1975-11-24 1977-12-27 Rohm And Haas Company Process for increasing molecular weight of a polymer

Also Published As

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DE3160784D1 (en) 1983-09-29
DE3018081A1 (de) 1981-11-19
ATE4513T1 (de) 1983-09-15
EP0039794A1 (fr) 1981-11-18

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